Intramolecular thermal transformations of N-phthalimidoaziridines: 1,3-dipolar cyclo-addition and rearrangements*
- 139 Downloads
The intramolecular thermal cycloaddition of N-phthalimidoaziridines at multiple bonds of substituents with the intermediate formation of azomethine ylides leads to condensed pyrrole derivatives, in which the five-membered ring is adjacent to a five-, six-, or seven-membered ring. Rearrangements, which sometimes become the predominant reactions, compete with cycloaddition. Thus, aziridines with aryl substituents readily isomerize to give imines with a 1,2-shift of the phthalimide group to one of the carbon atoms. Aziridines with one electron-withdrawing substituent probably do not open to give 1,3-dipoles but rather undergo a Cope-type rearrangement involving the three-membered ring and C = O bond of the second substituent. Even in intramolecular reactions, very low activity is found for the cyano group triple bond and aromatic ring bonds as dipolarophiles.
Keywordsaziridines azomethine ylides benzoxepinopyrrole chromenoimidazole hexahydro-indenopyrroles 1,3-dipolar cycloaddition rearrangements
This work was carried out with the financial support of St. Petersburg State University (Grant No. 220.127.116.111).
- 5.M. A. Kuznetsov, L. M. Kuznetsova, J. G. Schantl, and K. Wurst, Eur. J. Org. Chem., 1309 (2001).Google Scholar
- 6.R. S. Atkinson and B. J. Kelly, J. Chem. Soc., Perkin Trans. 1, 1627 (1989).Google Scholar
- 7.R. S. Atkinson and J. R. Malpass, J. Chem. Soc., Perkin Trans. 1, 2242 (1977).Google Scholar
- 8.D. J. Anderson, T. L. Gilchrist, D. C. Horwell, and C. W. Rees, J. Chem. Soc. C, 576 (1970).Google Scholar
- 10.M. A. Kuznetsov and V. V. Voronin, Khim. Geterotsikl. Soedin., 219 (2011). [Chem. Heterocycl. Comp., 47, 173 (2011)].Google Scholar
- 11.E. V. Beletskii and M. A. Kuznetsov, Zh. Org. Khim., 45, 1237 (2009).Google Scholar
- 12.M. A. Kuznetsov, A. S. Pan'kova, A. V. Ushkov, and S. I. Selivanov, Zh. Org. Khim., 44, 1807 (2008).Google Scholar
- 13.A. S. Pan'kova, Abstr. Chem. Sci. Cand. Diss., St. Petersburg, Russia (2009).Google Scholar
- 15.H. D. K. Drew and H. H. Hatt, J. Chem. Soc., 16 (1937).Google Scholar